Recently, a polymerization process of Anilinium-Dodecyl Benzene Sulfonic Acid (DBSA) complex in an aqueous dispersion was developed in our laboratories. Simple mechanical mixing of the aqueous PANI-DBSA dispersion with a PVAc aqueous latex leads to highly conductive blends at low PANI-DBSA contents. The percolation threshold of the dried films is extremely low (similar to0.5 wt %). The combined aqueous PVAc/PANI-DBSA dispersions exhibit a gradually decreasing electrical conductivity accompanied by a gradually increasing viscosity, with the storage time. However, an aged cast film from these blends maintains its electrical conductivity with time. These phenomena are associated with acidic hydrolytic reactions of the ester group, resulting in the formation of vinyl acetate-vinyl alcohol copolymer and evolution of acetic acid, and also the interaction of the DBSA surfactant with the PVAc, causing swelling and disintegration of PVAc particles. A chemical structural model describing these changes with storage time is suggested.